Dihydro-p-thioazines of the anthraquinone series and process of making same



Patented Apr. 23, 1929.

UNITED STATES PATENT OFFICE.

GEORG KRKNZLEIN AND MARTIN CORELL, 0F HOCHST-ON-THE-MAIN, GERMANY, AS- SIGNORS TO GRASSELLI DYESTUFF CORPORATION, OF NEW YORK, N. Y., A COR- PORATION OF DELAWARE.

DIHYDRO-P-THIOAZINES OF THE ANTHRAQUINONE SERIES AND PROCESS OF MARIN G SAME.

No Drawing. Application filed December 15, 1926, Serial No. 155,100, and in Germany December 17, 1925.

The present invention relates to the preparation of dihydro-p-thioazines of the anthraquinone series.

In our copending U. S. patent application Ser. 155,099, of even date, we have described reaction-products obtainable by subjecting ortho-amino-anthraquinone-mercaptans or the alkali salts thereof to reaction with bodies of the following type:

wherein Hlg stands for a halogen-atom and X represents a halogen or the hydroxyl group. The ortho-aminoanthraquinone omega-halogenethylthioethers and the orthoaminoanthraquinone omega-hydroxy thioether thus obtained are capable of being converted into new compounds, which may be regarded as dihydro-pthioazines of the anthraquinone.

series. In general compounds of the follow mg formula S.CH2.CH2.X

wherein A represents an anthraquinone residue which may be substituted and. x represents halogen or the OH-group, the two sub- S-CHrGHaHlg HOOHgOHz-S (1) 1-amino-anthraquinone-2- (omega-bromo)-ethylthioether M. P. 145-147 C. of the following formula:

somomer is heated to boiling in trichlorobenzene with a small quantity of copper added. As soon as the color of the solution has changed from red to violet-red, the trichlorobenzene is disform.

tilled off with steam and the residue is recrystallized from methly-alcohol and chloro- The anthraquinone-l.Q-dihydro-pthioazine thus obtained melts at 168 170 C. and has most probably the following constitution:

It dissolves in concentrated sulfuric acid to a reddish-violet solution.

(2) 20 parts by weight .of 1-a1nino-4-ptolylamino anthraquinone 2 (omega bro- Ino) -ethylthioether of the following formula:

the color of the solution has changed from red to a pure blue. After having poured the solution in water and washed it until neutral a bluish-red paste is obtained which dyes acetate silk red tints of excellent fastness. In a dry state; this body is identical with that obtained according to Example (1) When the ring of the lA-diaminoanthraquinone-2-chlor-3 omega hydroxythioether of the formula:

aomcmon kHz is closed there is obtained a blue dyestuff and, when the ring of the 1.5-diaminoanthraquinone-ortho-diomega-hydroxy thioether of the formula O NH:

S.CHz.CHz.OH

1 is closed, a bordeaux-red dystuif.

are heated with 200 parts of trichloro-benzene, 4 parts of dehydrated soduim acetate and 2 parts of copper powder until the pure blue color of the solution has turned bluishgreen. After cooling,- the new base, which now presumably contains the dihydro-p-thioazine ring and has probably the following constitution -NH'CH:

I OH:

is isolated. v

(3) Ortho -aminoanthraquinone omegav hydroxy-thioether of the following formula:

S.CH:. CHLOE is heated to about 100 C. in 510 times the quantity of oleum of 10% strength until Instead of the oleum there may also be used sulfuric acid at an elevated temperature, or zinc chloride as a means for closing the ring or as an acid medium.

(4) 50 parts of dihydro-p-thioazine of the formula:

(5) 1 amino 4 p-tolylamino-authraquinone-2- (omega-hydroxy) -thioether of the following formula:

S-GHLOHi-OH (ilHs are dissolved in 5-10 times the quantity of oleum of 20% strength and this solution is heated to 8090' C. until it has become soluble in water. During this operation the color of the solution, which is at first violet, turns greyish-blue. Evidently sulfonation takes; place simultanenously with the closing of the ring. It has the probable formula v SOIH The dyestufl thus obtained, after being isolated in the usual manner, dyes wool in an acid bath green tints.

We claim: g

l. A process which comprises heating to a temperature between C. and 220 C. in the presence of a diluent and a condensing agent a compound of the following formula:

A/NH:

scmomx wherein A represents an anthraquinone residue which may be substituted and x halogen I or the ()H-group, the two substituents standing in ortho-position to each other and in ocl and ,B-position in the anthraquinone nuc ens.

2. A process which comprises heating to a temperature between 70 C. and 220 in the presence of a diluent and a condensing agent a compound of the following formula:

Y wherein it stands for halogen or the OH- group and Y stands for group and Y stands for hydrogen or. the -NH.aryl-CH group.

3. A process which comprises heatin to a temperature between 70 C. and 150 in the presence of an excess of concentrated sulfuric acid, until the mass has become soluble in water, a compound of the following formula:

wherein A represents an anthraquinone residue which may be substituted and x halogen or the (DH-group, the two substituents standing in ortho-position to each other and in ocand B-position in the anthraquinone nucleus.

4. A process which comprises heating to a temperature between 70 C. and 150 C. in the presence of an excessof concentrated sulfuric acid, until the mass has become soluble in water a compound of the following formula:

O NH:

semen wherein X stands for halogen or the OH- group and'Y stands for hydrogen or the -l IH.aryl-CI I group. 1

5. A process which comprises heating to a temperature between 80 C. and 90 C. in the presence of an excess of oleum of 20% strength until the mass has become soluble in water a compound of the following formula;

A /NH:

S.CHz.CH:.x

wherein A represents an anthraquinone resiwherein X stands for halogen or the OH- hydrogen or the -NH.aryl-CH group.

7. As new products; compounds of the following formula;

wherein Y stands for hydrogen or the -NH.ary1-CH group, said compounds being suitable dyestuffs for dyeing acetate silk. 15 v8. As new products, compounds of the 01- I lowing formula:

ELaryLCHa NHOOH:

s moH Y 40 said com ound being a duestuif soluble in water an dyeing wool in an acid bath green tints.

In testimony whereof we aflix our signatunes.

GEORG KRANZLEIN. MARTIN CORELL. 

